Treatment of hydrocarbon oils



Patented Apr. 10, 1934 PATENT OFFICE 1,954,478 TREATMENT OF HYDROCARBON OILS Gustav Egloff, Chicago,

Oil Products Company,

tion of South Dakota No Drawing.

Ill., assignor to Universal Chicago, 111., a corpora- Application February 14, 1930,

Serial No. 428,520

1 Claim.

This invention relates to a process for the treatment of hydrocarbon oils and refers more particularly to a process for the hydrogenation of oils at elevated temperatures.

Among the objects of the process is to increase the yield of the lower boiling products made by the thermal decomposition or cracking of higher boiling oils; to saturate in part the more highly unsaturated hydrocarbons, especially those which form gums, polymers, and other undesirable materials in the motor fuel; and to desulphurize in part the hydrocarbons to render them more suitable for motor fuel and to facilitate and reduce the cost of refining.

It is not the purpose of this invention necessarily to completely saturate the hydrocarbons of the olefin series to produce parafiin hydrocarbons, but rather to add hydrogen in regulated amounts. to the more highly unsaturated hydrocarbons for the aforementioned purposes.

In the specific embodiment of the present invention, the hydrocarbons treated are the nonvaporized liquid residues of the cracking process. Gasoline, which is the major product of the cracking process, contains highly unsaturated hydrocarbons which upon standing polymerize and oxidize to form gums, tars, and other undesirable substances. The presence of sulphur compounds in a motor fuel may result in destructive corrosion of the crank case and other-parts of the motor during combustion and may also result in the destructive corrosion of the cracking or distillation equipment.

Among the further objects of my invention is the minimizing of these objectionable features.

In the specific embodiment of the present invention, the hydrocarbons are treated in the liquid state, with especial application to the hydrogenation of the non-vaporized residue from the reaction and flash chamber of the cracking process. For example, the invention may be used in a process well known in the art wherein oil is heated in a continuous coil and discharged in a reaction chamber from which is withdrawn the vaporous products resulting from the distillate and cracking and a non-vaporized residue. The residue from the reaction chamber may be treated according to the present invention by passing same through an insulated pipe or vessel, introducing the finely divided hydride and steam at this stage or preferably by the application of external heat to the residue leaving the reaction chamber while in the presence of steam and the finely divided hydride preferably under pressure.

In one mode of operation the non-vaporized residue is discharged from the reaction chamber under pressure and is vaporized by its self-contained heat in a vessel at lower pressure, the

amount of vaporization depending upon the temsaturated portions including the pitchy and asphaltic material of the oil as well as with sulphur compounds, saturating in part the olefinic hydrocarbons and reducing some of the higher sulphur compounds to hydrogen sulphide which may readily be removed from the final products.

As examples of hydrides, I may use those of sodium, potassium, calcium, magnesium, zinc, aluminum, iron, tin and others, including alloys and amalgams. The oxides or metals formed by the reaction with steam have some catalytic 8.0- 3

tion in promoting the hydrogenation and desulphurization as well as assisting in the cracking. The use of finely divided metals has an additional advantage in that the finer the metal the greater the surface exposure and consequently the greater the velocity or rate of reaction.

In addition to the above i may also add molecular hydrogen to the materials undergoing reaction in order to assist in the reaction, or I may add gases containing hydrogen such as gases from oil cracking, coke oven gas, producer gas, natural gas, etc.

In operating the process of the invention I may make use of any conventional apparatus or equipment suitable for cracking, but preferably I make use of a cracking system consisting of heating tubes or elongated pipe or heating coil in combination with a reaction chamber, dephlegmator or fractionating means and the auxiliary cooling, condensing, and collecting devices. 1100 In the operation of the process I preferably return the reflux or distillates condensed in the dephlegmating or fractionating \means to the heating equipment for reconversion as well as auxiliary heating tubes for the mixture of non-vaporized residuum and hydrides and steam. The mixture in? also be returned to the primary heating u es.

Preferably the oil is heated to a cracking temperature, although my invention contemplates operating the process at lower temperatures also. Preferably the process is operated at atmospheric pressure or at super-atmospheric pressure, and may in some cases also be operated at reduced or sub-atmospheric pressures. Preferably I make use of super-atmospheric pressures ranging from '75 pounds to 3000 pounds, more or less, and at temperatures of from approximately 400 degrees to 1400 degrees F.

As an example of the process, 2'7 gravity Mid- Continent topped crude when subjected to a cracking temperature of approximately 935 degrees F. and a pressure of approximately 1000' pounds shows an approximate yield of gasoline of 55% in addition to approximately 40% of a practically sludge free fuel oil. About 5% of coke and gas are also produced. The sulphur content of the gasoline produced, which would normally be approximately 0.3%, may be'reduced to approximately 0.1%.

The above example is illustrative and is not intended to be fully descriptive of the broad possibilities of the process and hence should not be construed as a limitation upon the process.

I claim as my invention: i

I A method for hydrogenating' residuum produced in the pressure cracking of hydrocarbon oils which comprises removing the residuum from the cracking process and adding thereto, while still in heated condition, a metallic hydride in 'finely divided form, and subjecting the resultant mixture to hydrogenating conditions of temperature and pressure in the presence of steam.

GUSTAV EGLOFF. 

